Method for defoaming cementitious compositions using polyamine oxides

ABSTRACT

The present invention provides a composition and method for controlling air voids in aqueous systems such as paints, coatings, sealants, adhesives, mastics, cements, mortar, masonry, or concrete, which comprises the reaction product of an oxidizing agent and a compound comprising at least one polyalkoxylated polyalkylene polyamine, at least one polyalkyoxylated polyethyleneimine, or a mixture thereof.

This application is a divisional of U.S. patent application Ser. No.14/716,139 filed May 19, 2015, the disclosure of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to agents for modifying air in an aqueouscomposition, and more particularly to a novel class of air managementcompositions based on polyalkoxylated polyamine oxides for controllingair content and quality, over a relatively wide pH range, within aqueoussystems, such as paints, sealants, coatings, concrete, mortar, masonry,or other aqueous compositions.

BACKGROUND OF THE INVENTION

It is known to employ amine defoamers for modifying air content andquality within aqueous environments such as hydratable cement andconcrete.

In U.S. Pat. No. 8,187,376, owned by the common assignee hereof, Kuotaught additive compositions for controlling air in cementitiouscompositions wherein a polyalkoxylated polyalkylene polyamine defoameris used in combination with certain air-entraining agents, such asalkanolamine compounds, oxyalkylene-containing water reducing orplasticizing agents, and other agents. In the '376 patent, Kuo explainedthat these compounds improve the stability of air-entraining additivesused in cement and concrete mixes, but without curtailing theeffectiveness of defoaming additives.

The present invention reflects the continued pursuit of the challenge todiscover a novel and unexpected defoaming agent which is highly stableand effective in aqueous systems such as cement, mortar, masonry, andconcrete, due to applicability over wide pH ranges, as well as inaqueous compositions such as paints, latexes and emulsions (e.g.,polymer latexes or emulsions), primers, sealants, adhesives, mastics,and others.

SUMMARY OF THE INVENTION

The present invention provides novel composition and method formodifying the content and quality of air in aqueous compositions, suchas paints, primers, sealants, adhesive, mastic, and other aqueouscompositions, and also including hydratable cementitious compositionssuch as cement, concrete, mortar, and masonry compositions.

The present inventors have surprisingly discovered that the use of anoxidized polyalkoxylated polyamine provides beneficial air detrainingcharacteristics in aqueous environments such cement or concretecompositions. This behavior is unexpected because alkylamine oxidesurfactants otherwise typically entrain air rather than detrain it. Thepolyalkoxylated polyamine oxides provide exceptional stability andsolubility in aqueous systems, and demonstrate excellent compatibilitywhen used with conventional concrete admixtures over an extended pHrange, including neutral and high pH (>7) environments.

An exemplary composition of the invention comprises the reaction productof at least one oxidizing agent and a compound comprising at least onepolyalkoxylated polyalkylene polyamine, at least one polyalkyoxylatedpolyethyleneimine, or mixture thereof; the at least one polyalkoxylatedpolyalkylene polyamine being represented by structural formula A

and the at least one polyalkoxylated polyethyleneimine being representedby structural formula B,-(AO)_(x)-(EI)_(y)-  [Formula B],wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ each individually represents ahydrogen, C₁-C₆ alkyl group, —CH₂—OH group, or -(AO)_(x)—R⁸ group; AOrepresents an alkylene oxide group selected from ethylene oxide (“EO”),propylene oxide (“PO”), butylene oxide (“BO”), or a mixture thereof,wherein the relative molar amount of EO compared to other alkyleneoxides within AO is zero percent to less than fifty percent of thetotal, and wherein the total sum of the number of EO and PO groupsexceeds 25; n represents an integer of 0 to 20; x represents an integerof 1 to 100; R⁸ represents hydrogen or a C₁-C₆ alkyl group; -(EI)_(y)—represents repeating ethyleneimine units in a linear or branchedstructure; y represents an integer of 5 to 100; and the relative numberof -(AO)_(x)— chains per repeating ethyleneimine unit is 0.1 to 1.0.

In exemplary embodiments of the invention, the reaction product is anoxide derived from ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, propylenediamine, dipropylene triamine, tripropylene tetramine, tetrapropylenepentamine, pentapropylene hexamine, N,N-dimethylethylene diamine,N,N′-dimethylethylene diamine, N,N-dimethylpropylene diamine,N,N′-dimethylpropylene diamine, N,N-diethylethylene diamine,N,N′-diethylethylene diamine, N,N-diethylpropylene diamine,N,N′-diethylpropylene diamine, or a mixture thereof. Most preferred arethe oxides derived from ethylene diamine, diethylene triamine,triethylene tetramine, or mixture thereof.

Another exemplary composition of the invention comprises theabove-described oxidized polyalkoxylated polyamine and one or more airentraining agents which entrain air in an aqueous environment. Foraqueous cementitious environments such as mortar and concrete slurriesor pastes, the air entraining agent may comprise a highertrialkanolamine, a lignosulfonate, a sulfonated naphthalene formaldehydecondensate, a sulfonated melamine formaldehyde condensate, anoxyalkylene-containing superplasticizer, an oxyalkylene-containingshrinkage reducing agent, or a mixture thereof.

While the oxidized polyalkoxylated polyamine may be introduced into theaqueous environment separately, it is more preferably introduced intothe aqueous environment of the mortar or concrete along with the atleast one air entraining agent, as a formulated admixture producthaving, as previously mentioned, a beneficial compatibility itscomponents, thereby conferring advantageous stability for purposes oftransportation, storage, or dispensing of the formulated product acrossa relatively wide pH range.

The present invention is further directed to aqueous compositions whichcontain the aforementioned oxidized polyalkoxylated polyamine, with orwithout air entraining agents, as well as to methods for modifyingaqueous environments, such as aqueous coatings, paints, adhesives,cements, concretes, and the like, using the aforesaid oxidizedpolyalkoxylated polyamine with or without air entraining agents.

Further features and benefits of the present invention are set forth indetail hereinafter.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

As summarized above, oxidized polyalkoxylated polyamine compositions ofthe present invention are useful for detraining air in aqueouscompositions such as water-based paints (e.g., polymer paints), primers,mastics, sealants, adhesives, and other aqueous compositions. Reducedair voids can lead to reduced pin-hole effects, and hence higher barrierproperties, such as when the coating composition hardens or cures into aprotective coating layer on a building or construction surface.

Exemplary aqueous compositions of the present invention includewater-based paints, such as acrylic paints (or paints which employ otherpolymers or resins). Given their relatively wide pH application range,the polyalkoxylated polyamine oxide compounds of the present inventioncan be used in coating compositions for building or constructionsurfaces which require alkali resistance, such as cement and concrete,fresh masonry, stucco, and plaster, as well as onto brick, stone, andmasonry blocks (which may comprise or contact cement or mortar).

An exemplary coating composition of the invention comprises (i) a bindermaterial (such as a polymer or resin) operative to form a coating upon asurface when applied thereto as a liquid aqueous coating composition andallowed to dry, and (ii) the oxidized polyalkoxylated polyaminecomposition as summarized previously in the Summary of the Invention,optionally with one or more air entraining additives. Exemplary polymersor resins can include an acrylic, polyurethane, rubber (e.g., styrenebutyl rubber), or other water-dispersible material which agglomerates,cross-links, bonds together, and/or otherwise forms a monolithic coatinglayer upon a surface when applied as a liquid aqueous coatingcomposition and allowed to dry and/or harden. The coating compositionmay be a solution, latex or emulsion, or other flowable orliquid-applied form which may be brushed, troweled, sprayed, rolled, orotherwise applied.

The polyalkoxylated polyamine oxides of the present invention areparticularly beneficial when used in the form of additive (admixture)compositions for detraining air within hydratable cementitiouscompositions such as cement, mortar, masonry, and concrete compositions.

The term “cement” as used herein includes hydratable cement which isproduced by pulverizing clinker consisting of hydraulic calciumsilicates and one or more forms of calcium sulfate (e.g., gypsum) as aninterground additive. “Mortars” are cement pastes formed with water andadditionally including fine aggregate (e.g., sand). “Concretes” aremortars which additionally include coarse aggregate (e.g., crushedstones or gravel).

The term “cementitious” as used herein refers to materials that includeor comprise cement (e.g., Portland cement) or which otherwise functionas a binder to hold together fine aggregates (e.g., sand), coarseaggregates (e.g., crushed gravel), or mixtures thereof. Typically,Portland cement is combined with one or more other supplementarycementitious materials (“SCMs”) and provided as a blend. SCMs mayinclude limestone, hydrated lime, fly ash, granulated blast furnaceslag, and silica fume, or other materials commonly included in suchcements. Cementitious materials may therefore include one or more SCMspreferably in an amount of 0%-100%, more preferably 10%-60%, based ontotal dry weight of cementitious material.

The term “hydratable” as used herein is intended to refer to cement orcementitious materials that are hardened by chemical interaction withwater. Portland cement clinker is a partially fused mass primarilycomposed of hydratable calcium silicates. The calcium silicates areessentially a mixture of tricalcium silicate (3CaO·SiO2 “C3S” in cementchemists notation) and dicalcium silicate (2CaO·SiO2, “C2S”) in whichthe former is the dominant form, with lesser amounts of tricalciumaluminate (3CaO·Al2O3, “C3A”) and tetracalcium aluminoferrite(4CaO·Al2O3·Fe2O3, “C4AF”). See e.g., Dodson, Vance H., ConcreteAdmixtures (Van Nostrand Reinhold, New York N.Y. 1990), page 1.

In various embodiments of the invention, the polyalkoxylated polyamineoxides can be used as a defoaming agent within an aqueous composition.

An exemplary embodiment relates to an additive or admixture formodifying a hydratable cementitious composition, wherein the additivecomprises at least one air entraining agent and the polyalkoxylatedpolyamine oxide. Examples of air entraining agents include a highertrialkanolamine, a lignosulfonate, a naphthalene sulfonate, a melaminesulfonate, an oxyalkylene-containing superplasticizer, anoxyalkylene-containing shrinkage reducing agent, or a mixture thereof.The term “additive” shall be used herein to describe additives added atthe cement manufacturing plant and also to describe “admixtures” whichare added to cement, water, and optional aggregates used for makingcement mortars, concretes, and other cementitious materials. Preferably,the additive compositions are aqueous liquids that may be dispensed(e.g., pump-metered) in liquid form.

The term “higher trialkanolamine” as used herein shall refer to tertiaryamine compounds which are tri(hydroxyalkyl) amines having at least oneC3-C5 hydroxyalkyl, and, more preferably, at least one C3-C4hydroxyalkyl, group therein. The remaining (if any) hydroxyalkyl groupsof the tertiary amine can be selected from C1-C2 hydroxyalkyl groups(preferably C2 hydroxyalkyl). Examples of such compounds includehydroxyethyl di(hydroxypropyl)amine, hydroxypropyldi(hydroxyethyl)amine, tri(hydroxypropyl)amine, hydroxyethyldi(hydroxy-n-butyl)amine, tri(2-hydroxybutyl)amine, hydroxybutyldi(hydroxypropyl)amine, and the like. The preferred highertrialkanolamines are triisopropanolamine (“TIPA”),N,N-bis(2-hydroxyethyl)-N-(2-hydroxypropyl)amine (“DEIPA”),N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (“EDIPA”), andtri(2-hydroxybutyl) amine. Mixtures of such higher trialkanolamines canbe used, and any of these or a combination of these can be used with oneor more of triethanolamine (TEA), diethanolamine (DEA),monoethanolamine, or mixtures thereof. When used as a grinding additivefor Portland cement or blended cement, the higher trialkanolamines canbe added in an amount up to 2%, preferably up to 0.1%, and mostpreferably between 0.005%-0.03% based on weight of the cement. Inparticular, TIPA is known for use as a late strength enhancer.

The terms “lignosulfonate,” “naphthalene sulfonate,” “melaminesulfonate,” and “oxyalkylene-containing superplasticizer” are usedherein to refer to water-reducing agents (“WRA”) known to entrain air. A“lignosulfonate” WRA includes alkali metal or alkaline earth salts oflignosulfonic acid, such as calcium lignosulfonate, which is acommonly-used WRA. A “naphthalene sulfonate” WRA includes an alkalimetal salt of a sulfonated naphthalene-formaldehyde condensate; while a“melamine sulfonate” WRA includes an alkali metal salt of a sulfonatedmelamine-formaldehyde condensate.

References to compounds in their salt form may be understood to includereference to their acid form, and vice-versa, because it may be the casethat both acid and salt forms can co-exist within the aqueousenvironment. Similarly, it may also be understood that reference tocompounds in their amine form may be understood to include reference totheir ammonium form, and vice-versa.

The term “oxyalkylene-containing superplasticizer” will refer towater-reducing agents, typically comb polymers comprised ofpolycarboxylic acid or partial esters to which are attached pendantpolyoxyalkylene groups. Such oxyalkylene groups include ethylene oxide(EO), propylene oxide (PO), and butylene oxide (BO). Suchoxyalkylene-containing superplasticizer will be any of those customarilyused in the cement and concrete industries. For example, polymericsuperplasticizers which are comb polymers having a carbon-containingbackbone to which are attached polyoxyalkylene groups through amide,imide, ester, and/or ether linkages are contemplated for use in thepresent invention. Other examples of oxyalkylene-containingsuperplasticizers include copolymers of acrylic or methacrylic acid withthe reaction product of acrylic acid or methacrylic acid withpolyalkyleneglycol monomethyl ether. A further example ofoxyalkylene-containing superplasticizers includes copolymers of acrylicacid or methacrylic acid with polyalkoxylated alcohols with typicalalcohol chain lengths of C3 to C20.

Generally, the amount of air-entraining water reducing agent (WRA) usedin the invention which is to be added to cement compositions will be inamounts of at least about 0.005 weight percent, and usually in the rangeof 0.005 to about 5 weight percent, and preferably 0.03 weight percentto about 1 weight percent based on the total weight of the cement orcementitious composition.

Exemplary compositions of the present invention, as previouslysummarized, comprise the reaction product of at least one oxidizingagent and a compound comprising at least one polyalkoxylatedpolyalkylene polyamine, at least one polyalkyoxylated polyethyleneimine,or mixture thereof; the at least one polyalkoxylated polyalkylenepolyamine being represented by structural formula A

and the at least one polyalkoxylated polyethyleneimine being representedby structural formula B,-(AO)_(x)-(EI)_(y)—  [Formula B],wherein R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ each individually represents ahydrogen, C₁-C₆ alkyl group, —CH₂—OH group, or -(AO)_(x)—R⁸ group; AOrepresents an alkylene oxide group selected from ethylene oxide (“EO”),propylene oxide (“PO”), butylene oxide (“BO”), or a mixture thereof,wherein the relative molar amount of EO compared to other alkyleneoxides within AO is zero percent to less than fifty percent of thetotal; n represents an integer of 0 to 20; x represents an integer of 1to 100; the sum total of the number of EO and PO groups exceeding 25; R⁸represents hydrogen or a C₁-C₆ alkyl group; -(EI)_(y)— representsrepeating ethyleneimine units in a linear or branched structure; yrepresents an integer of 5 to 100; and the relative number of -(AO)_(x)—chains per repeating ethyleneimine unit is 0.1 to 1.0.

It is preferred that exemplary reaction products of the presentinvention, as formed from oxidation of the polyalkoxylated polyamine asdescribed above, do not contain linear or branched alkyl groupsexceeding six carbons in length, as higher alkyl groups will tend toform a hydrophobic fatty group that tends to entrap air bubbles in themanner of a detergent within the aqueous environment into which thereaction product compound is introduced. Thus, the reaction product ofthe at least one oxidizing agent and compound comprising at least onepolyalkoxylated polyalkylene polyamine, at least one polyalkyoxylatedpolyethyleneimine, or mixture thereof, is preferably devoid of a linearor branched alkyl group having greater than six (6) carbon atoms, and,more preferably, devoid of a linear or branched alkyl group havinggreater than four (4) carbon atoms.

Exemplary oxidizing agents suitable for use in the present inventioninclude, but are not limited to, hydrogen peroxide, peroxyacids such asperformic acid, peracetic acid, perbenzoic acid, chloroperoxybenzoicacid, monoperphthalic acid, perfsulfuric acid, molecular oxygen, andozone.

Although the optimum degree of oxidation of the tertiary amine defoamerwill vary depending on the specific application and depending on themolecular weight and chemical structure of the starting polyalkoxylatedpolyamine material, 10 molar percent to 100 molar percent of thetertiary amine groups should preferably be oxidized into amine oxidegroups, and, more preferably, 20 molar percent to 100 molar percent ofthe tertiary amine groups should be oxidized into amine oxide groups.

In preferred exemplary embodiments, the defoamer is made by oxidation ofa polyalkoxylated polyalkylene polyamine. Exemplary polyalkylenepolyamines suitable for use in the present invention include, but arenot limited to, ethylene diamine, diethylene triamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, propylenediamine, dipropylene triamine, tripropylene tetramine, tetrapropylenepentamine, pentapropylene hexamine, N,N-dimethylethylene diamine,N,N′-dimethylethylene diamine, N,N-dimethylpropylene diamine,N,N′-dimethylpropylene diamine, N,N-diethylethylene diamine,N,N′-diethylethylene diamine, N,N-diethylpropylene diamine,N,N′-diethylpropylene diamine. More preferred of these polyalkylenepolyamines are ethylene diamine, diethylene triamine, triethylenetetramine, or mixtures thereof, with the most preferred being diethylenetriamine.

In other exemplary embodiments, the polyalkoxylation is carried out byreacting the polyalkylene polyamine with ethylene oxide, propyleneoxide, or a higher alkylene oxide. In still further exemplaryembodiments, the polyalkylene polyamine may be alkoxylated by reactingit with ethylene oxide and propylene oxide and/or butylene oxide,wherein the molar ratio of propylene oxide group(s) and/or butyleneoxide group(s) to ethylene oxide group(s) is greater than 1; and whereinthe sum total of the number of EO and PO groups exceeds 25. In anotherpreferred embodiment, the amount of ethylene oxide groups is in therange of 0%-40% based on total weight of the polyethers, whereas theamount of propylene oxide groups and/or butylene oxide groups is in therange of 60%-100% based on total weight of the polyethers.

In further exemplary embodiments, the oxidized polyalkoxylatedpolyalkylene polyamine defoamer of component A has a number-averagemolecular weight of 500-7,000. More preferably, the number-averagemolecular weight is 1,000-6,000; and most preferably the number-averagemolecular weight is 2,000-4,000.

In further exemplary embodiments, the defoamer is made by oxidation ofpolyalkoxylated polyethyleneimine. The polyethyleneimine orpolyaziridine can have linear and/or branched chemical structure and hasa number-average molecular weight in the range of 400 to 5,000.

In further exemplary embodiments, the oxidized polyalkoxylatedpolyethyleneimine defoamer of component B has a number-average molecularweight of 1,000-15,000. More preferably, the number-average molecularweight is 2,000-10,000; and most preferably the number-average molecularweight is 3,000-7,000.

In exemplary embodiments of the present invention, the polyalkoxylatedpolyamine oxide defoaming agent, obtained as the reaction product asdescribed above, may be incorporated separately into an aqueousenvironment, such as a paint, coating composition, or hydratablecementitious composition, such as mortar or concrete, separately or incombination with air entraining materials.

While the invention is described herein using a limited number ofembodiments, these specific embodiments are not intended to limit thescope of the invention as otherwise described and claimed herein.Modification and variations from the described embodiments exist. Morespecifically, the following examples are given as a specificillustration of embodiments of the claimed invention. It should beunderstood that the invention is not limited to the specific details setforth in the examples.

EXAMPLE 1 Synthesis of Amine Oxide

Polypropoxylated diethylene triamine with a number-average molecularweight (M_(n)) of 2,550 (100 g, 0.039 mol), n-propanol (50 ml) andacetic acid (0.2 g) were added into a reaction vessel. The mixture washeated with stirring to 50° C., and then 30 wt % aqueous hydrogenperoxide solution (4.54 g, 0.04 mol) was dropped into the mixture over aperiod of 40 min at 50-55° C. After hydrogen peroxide addition, themixture was kept at 60-65° C. with stirring for 18 hours. The resultingamine oxide product (sample AO1) was collected by removing n-propanolsolvent using a rotary evaporator.

Amine oxide sample AO2 and AO3 were synthesized in a similar fashionwith increased amounts of hydrogen peroxide (Table 1).

TABLE 1 (Synthesized Amine Oxides) Amine oxide 30 wt % aqueous productStarting tertiary amine (g) hydrogen peroxide (g) Sample AO1Polypropoxylated diethylene triamine 4.54 (M_(n) 2,550), 100 Sample AO2Polypropoxylated diethylene triamine 9.08 (M_(n) 2,550), 100 Sample AO3Polypropoxylated diethylene triamine 13.6 (M_(n) 2,550), 100

EXAMPLE 2 Formulation Stability

In this example, the stability of different defoamer additive in a lowpH admixture containing polycarboxylate ether dispersant was evaluated.The admixtures containing defoamers were prepared according to therecipe in Table 2. Water (32.9 g), Sample AO1 (0.40 g) and 60% aqueouspolycarboxylate dispersant solution (66.7 g) were added into a beakerunder stirring, then the mixture was stirred until it becamehomogeneous. The pH of this mixture was adjusted to 3.5-4.0 with aceticacid. The mixture was kept in 50 ml cylinders both in 25° C. and 50° C.ovens while its stability was monitored visually for 30 days or untilphase separation occurs.

TABLE 2 (Admixture Stability Test) Polycarboxylate Stability etherdispersant (day)^(a) Entry solution (g) Additive (g) pH 25° C. 50° C. 166.7 Polypropoxylated 0.4 3.7 30 30 diethylene triamine (M_(n) 2,550) 266.7 Sample AO1 0.4 3.7 30 30 3 66.7 Sample AO2 0.4 3.7 30 30 4 66.7Sample AO3 0.4 3.7 30 30 ^(a)Stability is represented by the time beforephase separation is observed within a maximum of 30 days.

From Table 2, it is evident that the amine oxide defoamer additives AO1,AO2 and AO3 are equally stable in admixtures with their starting aminematerial under acidic condition.

EXAMPLE 3 Formulation Stability

In this example, the stability of different defoamer additive wasevaluated in a neutral pH admixture containing polycarboxylate etherdispersant. The admixtures containing defoamers were prepared accordingto the recipe in Table 3. Water (19.6 g), Sample AO1 (0.40 g) and 50%aqueous polycarboxylate ether dispersant solution (80 g) were added intoa beaker under stirring, then the mixture was stirred until it becamehomogeneous. The resultant mixture has a pH value between 6.25 and 7.0.The admixture was kept in 50 ml cylinders in 25° C. and 50° C. ovens,and their stability was monitored visually over 30 days or until phaseseparation occurs.

TABLE 3 (Admixture Stability Test) Polycarboxylate ether dispersantStability (day)^(a) Entry solution (g) Additives (g) pH 25° C. 50° C. 580 Polypropoxylated 0.4 6.7 <1 <1 diethylene triamine (M_(n) 2,550) 6 80Sample AO1 0.4 6.6 2 <1 7 80 Sample AO2 0.4 6.6 18 5 8 80 Sample AO3 0.46.7 21 10 ^(a)Stability is represented by time elapsed before phaseseparation is observed within a maximum of 30 days.

As evidenced in Table 3, the amine oxide defoamer additives are morestable in admixtures compared to their starting amine material underneural pH condition.

EXAMPLE 4 Formulation Stability

In this example, the stability of different defoamer additive wasevaluated in a high pH admixture containing polycarboxylate etherdispersant and set accelerants. The admixtures were prepared accordingto the recipe in Table 4. Water (76.1 g), 60% aqueous polycarboxylateether dispersant solution (13.3 g), and sodium hydroxide (0.4 g) wereadded into a beaker under stirring. After fully mixing, the resultantmixture has a pH above 8. Then calcium nitrite (5.6 g, 32% solution),sodium thiocyanate (4.0 g, 50% solution) and Sample AO1 (0.2 g) wereadded into the admixture and stirred until it became homogeneous. The pHof the final admixture solution was adjusted with sodium hydroxide to8.5-9.5. The admixture was kept in 50 ml cylinders in 25° C. and 50° C.ovens, and their stability was monitored visually over 30 days or untilphase separation occurs.

TABLE 4 (Admixture Stability Test^(a)) Polycarboxylate ether dispersantStability (day)^(b) Entry solution (g) Additives (g) pH 25° C. 50° C.  913.3 Polypropoxylated 0.2 9.0 <1 <1 diethylene triamine (M_(n) 2,550) 1013.3 Sample AO1 0.2 9.1 30 9 11 13.3 Sample AO2 0.2 9.1 30 10 12 13.3Sample AO3 0.2 9.0 30 5 ^(a)All admixture contain sodium hydroxide (0.4g), 36 wt % calcium nitrite solution (5.6 g) and 50 wt % sodiumthiocyanate solution (4.0 g). ^(b)Stability is represented by the timeelapsed before phase separation is observed within a maximum of 30 days.

The results in Table 4 clearly indicate that the admixtures containingthe amine oxide defoamer additives of the present invention are muchmore stable in than the admixture containing the starting amine defoamerunder alkaline condition.

EXAMPLE 5 Mortar Air Testing

In this example, the defoaming efficacy of different amine oxide wasevaluated in standard mortar test for workability and air content, andthe mortar air content was measured in accordance with ASTM C185-02standard. The composition of mortar was as following: cement (540 g),sand (1400 g), polycarboxylate dispersant (0.9 g, 60 wt %), defoameradditive (0.011 g), and water (225 g).

TABLE 5 (ASTM C185 Mortar Air Test^(a)) Workability Air Entry Additives(g) (mm) (%) 13 none 0 273 10.2 14 Polypropoxylated diethylene 0.011 2553.1 triamine (M_(n) 2,550) 15 Sample AO1 0.011 253 2.7 16 Sample AO20.011 252 2.7 17 Sample AO3 0.011 246 3.0 18 Comparative Additive:Dimethyl 0.011 253 18.6 tetradecylamine oxide

By comparing entries 15, 16 and 17 to entry 13 in Table 5, it was clearthat the claimed amine oxide defoamers, Samples AO1˜AO3 were effectivein reducing air content in mortar. On the contrary, dimethyltetradecylamine oxide, in entry 18 of Table 5, did not have defoamingabilities; it increased mortar air content.

EXAMPLE 6 Concrete Air Testing

In this example, the defoaming efficacy of different amine oxide wasevaluated in concrete against the polypropoxylated diethylene triaminestarting material. Concrete mixes were carried out according to thefollowing composition: ordinary Portland cement, 11.7 kg; water, 4.48kg; coarse aggregate, 29.1 kg; fine aggregate, 25.1 kg; polycarboxylateether dispersant (60 wt % solution), 17 g; commercial air-entrainingagent DARAVAIR® 1000, 1.2 g; and amine oxide additive or amine additiveas listed. Air content was measured in accordance with ASTM C231-97. Theresults were summarized in Table 6.

TABLE 6 Concrete test Entry Additive (g) Air (%) 19 none 0 8.5 20Polypropoxylated diethylene 0.3 3.4 triamine (M_(n) 2,550) 21 Sample AO10.3 3.8 22 Sample AO2 0.3 4.2

The data in Table 6 clearly indicate that the amine oxide of theinvention (entries 21 and 22) are effective defoamers in reducing aircontent in concrete (compared to entry 19).

The foregoing example and embodiments were present for illustrativepurposes only and not intended to limit the scope of the invention.

It is claimed:
 1. A method for modifying air properties in acementitious composition, comprising: adding to a hydratablecementitious composition a reaction product of at least one oxidizingagent and a compound comprising at least one polyalkoxylatedpolyalkylene polyamine, at least one polyalkyoxylated polyethyleneimine,or a mixture thereof; the at least one polyalkoxylated polyalkylenepolyamine represented by structural formula A

and the at least one polyalkoxylated polyethyleneimine represented bystructural formula B,-(AO)_(x)-(EI)_(y)—  [Formula B], wherein n represents an integer of 0to 4; R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ each individually represents ahydrogen, C₁-C₆ alkyl group, —CH₂—OH group, or -(AO)_(x)—R⁸ group,wherein at least two of R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ groups representsan -(AO)_(x)—R⁸ group, except that if n=0 then at least two of the R¹,R², R³, R⁴, R⁶, and R⁷ groups represents an -(AO)_(x)—R⁸ group; AOrepresents an alkylene oxide group chosen from ethylene oxide, propyleneoxide, butylene oxide, or a mixture thereof, wherein the relative molaramount of ethylene oxide compared to other alkylene oxide groups withinAO is zero percent to less than fifty percent of the total; wherein thetotal sum of the number of ethylene oxide and propylene oxide groupsexceeds 25; wherein x represents an integer of 26 to 100; wherein R⁸represents hydrogen or a C₁-C₆ alkyl group; wherein -(EI)_(y)—represents repeating ethyleneimine units in a linear or branchedstructure; wherein y represents an integer of 5 to 100; wherein therelative number of (AO)_(x)— groups per repeating ethyleneimine unit is0.1 to 1.0; and wherein the reaction product of the at least oneoxidizing agent and the compound comprising the at least onepolyalkoxylated polyalkylene polyamine or the at least onepolyalkoxylated polyethyleneimine is effective for modifying air withinthe cementitious composition and is devoid of a linear or branched alkylgroup having greater than six carbon atoms which would function toentrain air within the cementitious composition.
 2. The method of claim1 wherein the reaction product of the at least one oxidizing agent andthe compound comprising at least one polyalkoxylated polyalkylenepolyamine is derived from polyalkoxylated product of ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene pentamine,pentaethylene hexamine, propylene diamine, dipropylene triamine,tripropylene tetramine, tetrapropylene pentamine, pentapropylenehexamine, N,N-dimethylethylene diamine, N,N′-dimethylethylene diamine,N,N-dimethylpropylene diamine, N,N′-dimethylpropylene diamine,N,N-diethylethylene diamine, N,N′-diethylethylene diamine,N,N-diethylpropylene diamine, N,N′-diethylpropylene diamine, or amixture thereof.
 3. The method of claim 1 wherein the reaction productof the at least one oxidizing agent and the compound comprising at leastone polyalkoxylated polyalkylene polyamine is derived frompolyalkoxylated product of ethylene diamine, polyalkoxylated diethylenetriamine, triethylene tetramine, or mixture thereof.
 4. The method ofclaim 1 wherein the at least one oxidizing agent is selected from thegroup consisting of hydrogen peroxide, performic acid, peracetic acid,perbenzoic acid, chloroperoxybenzoic acid, monoperphthalic acid,persulfuric acid, molecular oxygen, ozone, or mixture thereof.
 5. Themethod of claim 1 wherein the at least one oxidizing agent is hydrogenperoxide.
 6. The method of claim 1 wherein the reaction product is madefrom a compound comprising the at least one polyalkoxylated polyalkylenepolyamine having the structure of Formula A wherein the ethylene oxidegroups is 0% to 40% based on the total weight of the polyethers in thepolyalkoxylated polyalkylene polyamine.
 7. The method of claim 1 wherein10 molar percent to 100 molar percent of the tertiary amine groups ofthe polyalkoxylated polyalkylene polyamine having the structure ofFormula A is oxidized into amine oxide groups.
 8. The method of claim 1wherein the reaction product of at least one oxidizing agent and acompound comprising at least one polyalkoxylated polyalkylene polyaminehaving the structure of Formula A and a molecular weight of 500 to7,000.
 9. The method of claim 1 wherein the reaction product of at leastone oxidizing agent and a compound comprising at least onepolyalkoxylated polyalkylene polyamine having the structure of Formula Aand a molecular weight of 1,000 to 6,000.
 10. The method of claim 1wherein the reaction product of at least one oxidizing agent and acompound comprising at least one polyalkoxylated polyalkylene polyaminehaving the structure of Formula A and a molecular weight of 2,000 to4,000.
 11. The method of claim 1 further comprising mixing with thecementitious composition at least one agent effective to entrain air ina hydratable cementitious composition, the at least one agent comprisinga trialkanolamine, a lignosulfonate, a sulfonated naphthaleneformaldehyde condensate, a sulfonated melamine formaldehyde condensate,an oxyalkylene-containing superplasticizer, an oxyalkylene-containingshrinkage reducing agent, or a mixture thereof.
 12. A method formodifying air properties in a cementitious composition, comprising:adding to a hydratable cementitious composition a reaction product of atleast one oxidizing agent chosen from hydrogen peroxide, performic acid,peracetic acid, perbenzoic acid, chloroperoxybenzoic acid,monoperphthalic acid, persulfuric acid, molecular oxygen, ozone, ormixture thereof, and a compound comprising at least one polyalkoxylatedpolyalkylene polyamine represented by structural formula A

wherein n represents an integer of 0 to 4; wherein R¹, R², R³, R⁴, R⁵,R⁶, and Reach individually represents a hydrogen, C₁-C₆ alkyl group,—CH₂—OH group, or -(AO)_(x)—R⁸ group, wherein at least two of R¹, R²,R³, R⁴, R⁵, R⁶, and R⁷ groups represents an -(AO)_(x)—R⁸ group, exceptthat if n=0 then at least two of the R¹, R², R³, R⁴, R⁶, and R⁷ groupsrepresents an -(AO)_(x)—R⁸ group; wherein AO represents an alkyleneoxide group chosen from ethylene oxide, propylene oxide, or a mixture ofethylene oxide and propylene oxide; wherein the relative molar amount ofethylene oxide compared to other alkylene oxide groups within AO is zeropercent to less than fifty percent of the total; wherein the total sumof the number of ethylene oxide and propylene oxide groups exceeds 25;wherein x represents an integer of 26 to 100; wherein R⁸ representshydrogen or a C₁-C₆ alkyl group; wherein 10 molar percent to 100 molarpercent of the tertiary amine groups of the polyalkoxylated polyalkylenepolyamine is oxidized into amine oxide groups; and wherein the reactionproduct of the at least one oxidizing agent and the compound comprisingthe at least one polyalkoxylated polyalkylene polyamine is devoid of alinear or branched alkyl group having greater than six carbon atomswhich would function to entrain air within the cementitious composition.13. The method of claim 12 further comprising mixing with thecementitious composition at least one agent effective to entrain air ina hydratable cementitious composition, the at least one agent comprisinga trialkanolamine, a lignosulfonate, a sulfonated naphthaleneformaldehyde condensate, a sulfonated melamine formaldehyde condensate,an oxyalkylene-containing superplasticizer, an oxyalkylene-containingshrinkage reducing agent, or a mixture thereof.
 14. The method of claim13 wherein the at least one agent effective to entrain air in ahydratable cementitious composition is an oxyalkylene-containingsuperplasticizer.
 15. The method of claim 12 wherein the alkylene oxidegroup represented by AO and chosen from ethylene oxide, propylene oxide,or a mixture of ethylene oxide and propylene oxide further comprises atleast one butylene oxide group.